CA1297494C - Process for the preparation of dialkyl vinylphosphonates - Google Patents
Process for the preparation of dialkyl vinylphosphonatesInfo
- Publication number
- CA1297494C CA1297494C CA000560543A CA560543A CA1297494C CA 1297494 C CA1297494 C CA 1297494C CA 000560543 A CA000560543 A CA 000560543A CA 560543 A CA560543 A CA 560543A CA 1297494 C CA1297494 C CA 1297494C
- Authority
- CA
- Canada
- Prior art keywords
- reaction
- phosphonic acid
- range
- total
- dialkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 31
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical class OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 150000002148 esters Chemical class 0.000 claims abstract description 16
- 238000003776 cleavage reaction Methods 0.000 claims abstract description 9
- 230000007017 scission Effects 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 230000036647 reaction Effects 0.000 claims abstract description 4
- OHJGUUXFCGLGEB-UHFFFAOYSA-N C(C)(=O)OCC.P(O)(O)=O Chemical compound C(C)(=O)OCC.P(O)(O)=O OHJGUUXFCGLGEB-UHFFFAOYSA-N 0.000 claims abstract 6
- 238000004519 manufacturing process Methods 0.000 claims abstract 3
- 239000000047 product Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000000306 component Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 208000036366 Sensation of pressure Diseases 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 6
- -1 alkyl acetate Chemical compound 0.000 description 5
- KDNRMBNMFMHMRM-UHFFFAOYSA-N 1-acetyloxyethylphosphonic acid Chemical class OP(=O)(O)C(C)OC(C)=O KDNRMBNMFMHMRM-UHFFFAOYSA-N 0.000 description 4
- CQCXMYUCNSJSKG-UHFFFAOYSA-N 1-dimethoxyphosphorylethene Chemical compound COP(=O)(OC)C=C CQCXMYUCNSJSKG-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BLHKHXZFFILOIW-UHFFFAOYSA-N 1-dimethoxyphosphorylethyl acetate Chemical compound COP(=O)(OC)C(C)OC(C)=O BLHKHXZFFILOIW-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- ZTWTYVWXUKTLCP-UHFFFAOYSA-L ethenyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-L 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- DREPONDJUKIQLX-UHFFFAOYSA-N 1-[ethenyl(ethoxy)phosphoryl]oxyethane Chemical compound CCOP(=O)(C=C)OCC DREPONDJUKIQLX-UHFFFAOYSA-N 0.000 description 2
- YROIHKKJDMNYRB-UHFFFAOYSA-N 2-acetyloxyethylphosphonic acid Chemical class CC(=O)OCCP(O)(O)=O YROIHKKJDMNYRB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002905 orthoesters Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- DPXYOLOTFDZJPX-UHFFFAOYSA-N 1-diethoxyphosphorylethyl acetate Chemical compound CCOP(=O)(OCC)C(C)OC(C)=O DPXYOLOTFDZJPX-UHFFFAOYSA-N 0.000 description 1
- TUJWGDXCTRWVDC-UHFFFAOYSA-N 2-diethoxyphosphorylethyl acetate Chemical compound CCOP(=O)(OCC)CCOC(C)=O TUJWGDXCTRWVDC-UHFFFAOYSA-N 0.000 description 1
- JQOYXWMDISLLFO-UHFFFAOYSA-N 3-(2-carboxy-3-phosphonopropyl)benzoic acid Chemical compound OP(=O)(O)CC(C(=O)O)CC1=CC=CC(C(O)=O)=C1 JQOYXWMDISLLFO-UHFFFAOYSA-N 0.000 description 1
- 101150034533 ATIC gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical class [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
- 229940022663 acetate Drugs 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- PUSKHXMZPOMNTQ-UHFFFAOYSA-N ethyl 2,1,3-benzoselenadiazole-5-carboxylate Chemical compound CCOC(=O)C1=CC=C2N=[Se]=NC2=C1 PUSKHXMZPOMNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229910000064 phosphane Inorganic materials 0.000 description 1
- 150000003002 phosphanes Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical class OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4015—Esters of acyclic unsaturated acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract:
A process for the production of dialkyl esterr of vinyl phosphonic acid which comprises subjecting dialkyl esters of 2-acetoxyethane phosphonic acid to cleavage by contacting with a liquid catalytically acting medium at a temperature in the range from 150 to 270°C and under a pressure such that the partial pressures of the total of the components of the reac-tion system is in the range from 1 to 500 mbar, and drawing off the resultlng dialkyl esters of vinyl phosphonic acid and other volatile reaction products.
A process for the production of dialkyl esterr of vinyl phosphonic acid which comprises subjecting dialkyl esters of 2-acetoxyethane phosphonic acid to cleavage by contacting with a liquid catalytically acting medium at a temperature in the range from 150 to 270°C and under a pressure such that the partial pressures of the total of the components of the reac-tion system is in the range from 1 to 500 mbar, and drawing off the resultlng dialkyl esters of vinyl phosphonic acid and other volatile reaction products.
Description
~;~97~
,, HOECHST AKTIENGESELLSCHAFT HQ~ 87/F 065 Dr. Klr/MW
Description:
Process for the preparation of d;alkyl v;nylphos?honates DialkyL vinylphosphonates are of importance as precur-sors for the preparation of pure vinylphosphonic acid and also as monomers ~or copolymer;zat;on for the prepa-ration of adhesives or flameproof plast;cs. tt has hitherto been p~ssible to prepare them by var;ous routes, but only in mult;-stage procedures. Thus mixtures of vinylphosphonic acid derivatives which, in add;t;on to monoalkyl vinylphosphonates and several other produc~, also contain small quantities ~23X in the highest case) of dialkyl vinylphosphonate~ are obtained by the proc~ss of German Offenlegungsschrift 3,001,894 by heating dialkyl 2-acetoxyethanephosphonates at 150 to 270C in the pre-sence of ac;d or basic catalysts.
In vie~ of ~hese unsatisfactory results, this process has been superseded by an i~proved t~o-stage process according to German Offenlegungsschrift 3,120,437, in which the alkyl acetate elimina~ed in the abovementioned reaction is distilled off, and the reaction product ob-ta;ned as a bottom product is then reacted ~ith ortho-esters of carboxyl;c acids to give the desired dialkyl vinylphosphonates.
Thus none of the Literature references mentioned des-cribes the direct isolation of dialkyl vinylphosphonates which can be obtained as a distilLate from the cleavage re3ction and can subsequently be purified further by distillation.
It has no~ been found, surprisingly, that the cleavage of dialkyl acetoxyethanephosphonates does not take place in the ~anner described to ~ive ~ixtures o~ derivatives of vinylphosphonic acid, but gives dialkyl \
129~9~94 vinylphosphonates directly, if dialkyl ~-acetoxyethanephc~-phonates are cleaved at 150 to 270C, preferably at 180 ~o 250C, at a partial pressure of the sum of the components in the reaction syste~ bet~een 1 and 500 mbar, preferabLy bet~een 5 and 100 mbar, and in contact ~ith a liquid medium having a catalytic action, and if the dialkyl vinylphos-phonates and other voLat;le reaction products Sormed are re~oved in the form of vapor.
The express;on "partial pressure of the sum of the com-ponents in the reaction system" embraces both the pres-sure of the dialkyl 2-acetoxyethanephosphonate and that of the reaction products formed therefrom, which are for the most part more volatile than the starting material and ;n this respect can be removed from the mixture by distillation. The pressur0 mentioned, for example be t~een 10 and 100 mbar, c~n be obtained in various ~ays.
In one embodiment the reaction is carried out under re-duced pressure; in another procedure the reaction is carried out under a pressure of more than 500 mbar~ it being possible to produce the difference between the total pressure and the desired partial pressure ot the co~ponents in the reaction system by means of a gas ~hich is inert touards the latter under the conditions of the reaction. Suitable inert gases of this type are those ~hich are customary in practice, above all nitro-~en, but also, if appropriate, carbon dioxide or light hydrocarbons, such as methane or ethane, and, in special cases, also noble gases, such as argon. It is~ of course, aLso possible to use mixtures of various gases of this type~
Suitable med;a having a catalytic action are the same as those mentioned in German Offenlegungsschrift 3,120,437, specifically either acid or basic media.
Exaaples of suitable acid media are sulfur;c acid, phos-phoric acidr halogen-containing carboxylic acids, such as dichloroacetic'~nd trichloroacetic acids and also trifluoroacetic acid, aro~atic sulfonic acids, such as ~;297~9~
benzenesulfonic and p-toluenesulfonic acids and vinylphosphonic acid, but, above all, products which are obtained from the byproducts produced as a bottom pro-duct ;n the present reaction, iOe. higher-boiling by-products, by heating the latter with water, it beingpossibLe to carry out the treatment wi~h water by, for example, boiling for a period of 5 minutes to 2 hours.
Examples of basic media ~hich can be used are tert;ary aliphatic and aromatic amines and phosphanes (previously dessribed as phosphines), such as are also mentioned ;n large numbers in German Offenlegungsschrift 3,120,437~
The medium having a catalytic action is generally used in an amount of at least 0.1X by weight, relative to the dialkyl acetoxyethanephosphonate put through. The con-centration in the reaction mixture is, natu ally, sub-stantially higher, since it acts as the reaction medium~
In general, its amount is 1-20% by weight, it being, of course, preferable to use the smallest possible amounts, advantageously not more than 5X by weight, relative to th~ dialkyl acetoxyethanephosphonate put through. On the other hand, and this applies above all ~hen using the byproducts of the reaction according to the inven-tion which have been treated with ~ater, it is also Pos-sible to use the media having a catalytic action ina~ounts even Larger than 20% by weight without endanger-ing the ~easability of the reaction. The term % by weight relates in every case to the ~eight of dialkyl acetoxyethanephosphonate~
Although the present process is industrially suitable p~rticularly for the preparation of dimethyl vinylphos-phonate and diethyl vinylphosphonate, it is also pos-sible to prepare esters having alkyl groups with nore than two c3rbon atoms, such as propyL, isopropyl and the various butyl, pentyl~ hexyl, heptyl and octyl groups.
In general, therefore, the esters prepared in accor-dance ~ith the inven~ion contain alkyl groups having not m~re than 8, preferably not more than 4, carbon atoms, ~;2974~L
,, HOECHST AKTIENGESELLSCHAFT HQ~ 87/F 065 Dr. Klr/MW
Description:
Process for the preparation of d;alkyl v;nylphos?honates DialkyL vinylphosphonates are of importance as precur-sors for the preparation of pure vinylphosphonic acid and also as monomers ~or copolymer;zat;on for the prepa-ration of adhesives or flameproof plast;cs. tt has hitherto been p~ssible to prepare them by var;ous routes, but only in mult;-stage procedures. Thus mixtures of vinylphosphonic acid derivatives which, in add;t;on to monoalkyl vinylphosphonates and several other produc~, also contain small quantities ~23X in the highest case) of dialkyl vinylphosphonate~ are obtained by the proc~ss of German Offenlegungsschrift 3,001,894 by heating dialkyl 2-acetoxyethanephosphonates at 150 to 270C in the pre-sence of ac;d or basic catalysts.
In vie~ of ~hese unsatisfactory results, this process has been superseded by an i~proved t~o-stage process according to German Offenlegungsschrift 3,120,437, in which the alkyl acetate elimina~ed in the abovementioned reaction is distilled off, and the reaction product ob-ta;ned as a bottom product is then reacted ~ith ortho-esters of carboxyl;c acids to give the desired dialkyl vinylphosphonates.
Thus none of the Literature references mentioned des-cribes the direct isolation of dialkyl vinylphosphonates which can be obtained as a distilLate from the cleavage re3ction and can subsequently be purified further by distillation.
It has no~ been found, surprisingly, that the cleavage of dialkyl acetoxyethanephosphonates does not take place in the ~anner described to ~ive ~ixtures o~ derivatives of vinylphosphonic acid, but gives dialkyl \
129~9~94 vinylphosphonates directly, if dialkyl ~-acetoxyethanephc~-phonates are cleaved at 150 to 270C, preferably at 180 ~o 250C, at a partial pressure of the sum of the components in the reaction syste~ bet~een 1 and 500 mbar, preferabLy bet~een 5 and 100 mbar, and in contact ~ith a liquid medium having a catalytic action, and if the dialkyl vinylphos-phonates and other voLat;le reaction products Sormed are re~oved in the form of vapor.
The express;on "partial pressure of the sum of the com-ponents in the reaction system" embraces both the pres-sure of the dialkyl 2-acetoxyethanephosphonate and that of the reaction products formed therefrom, which are for the most part more volatile than the starting material and ;n this respect can be removed from the mixture by distillation. The pressur0 mentioned, for example be t~een 10 and 100 mbar, c~n be obtained in various ~ays.
In one embodiment the reaction is carried out under re-duced pressure; in another procedure the reaction is carried out under a pressure of more than 500 mbar~ it being possible to produce the difference between the total pressure and the desired partial pressure ot the co~ponents in the reaction system by means of a gas ~hich is inert touards the latter under the conditions of the reaction. Suitable inert gases of this type are those ~hich are customary in practice, above all nitro-~en, but also, if appropriate, carbon dioxide or light hydrocarbons, such as methane or ethane, and, in special cases, also noble gases, such as argon. It is~ of course, aLso possible to use mixtures of various gases of this type~
Suitable med;a having a catalytic action are the same as those mentioned in German Offenlegungsschrift 3,120,437, specifically either acid or basic media.
Exaaples of suitable acid media are sulfur;c acid, phos-phoric acidr halogen-containing carboxylic acids, such as dichloroacetic'~nd trichloroacetic acids and also trifluoroacetic acid, aro~atic sulfonic acids, such as ~;297~9~
benzenesulfonic and p-toluenesulfonic acids and vinylphosphonic acid, but, above all, products which are obtained from the byproducts produced as a bottom pro-duct ;n the present reaction, iOe. higher-boiling by-products, by heating the latter with water, it beingpossibLe to carry out the treatment wi~h water by, for example, boiling for a period of 5 minutes to 2 hours.
Examples of basic media ~hich can be used are tert;ary aliphatic and aromatic amines and phosphanes (previously dessribed as phosphines), such as are also mentioned ;n large numbers in German Offenlegungsschrift 3,120,437~
The medium having a catalytic action is generally used in an amount of at least 0.1X by weight, relative to the dialkyl acetoxyethanephosphonate put through. The con-centration in the reaction mixture is, natu ally, sub-stantially higher, since it acts as the reaction medium~
In general, its amount is 1-20% by weight, it being, of course, preferable to use the smallest possible amounts, advantageously not more than 5X by weight, relative to th~ dialkyl acetoxyethanephosphonate put through. On the other hand, and this applies above all ~hen using the byproducts of the reaction according to the inven-tion which have been treated with ~ater, it is also Pos-sible to use the media having a catalytic action ina~ounts even Larger than 20% by weight without endanger-ing the ~easability of the reaction. The term % by weight relates in every case to the ~eight of dialkyl acetoxyethanephosphonate~
Although the present process is industrially suitable p~rticularly for the preparation of dimethyl vinylphos-phonate and diethyl vinylphosphonate, it is also pos-sible to prepare esters having alkyl groups with nore than two c3rbon atoms, such as propyL, isopropyl and the various butyl, pentyl~ hexyl, heptyl and octyl groups.
In general, therefore, the esters prepared in accor-dance ~ith the inven~ion contain alkyl groups having not m~re than 8, preferably not more than 4, carbon atoms, ~;2974~L
it being also possibLe to employ~ and 3lso to prepare, mixed esters hav;ng different alkyl groups.
The process according to the invention can be carried 5 out discontinuously, but also, with particular advantage, cont;nuously5 the cleavage produc~s formed, especially the dialkyl vinylphosphonate, being removed cont;nuously from the reaction mixture by distillation~
It ~as surprising that, under the cond;~ions used in accordance w;th the ;nvention, the dialkyl vinyLPhos-phonates are obtained in a single process sta~e and in a high yield, al~hough in the processes of the state of the art the only reaction to take place, under a higher pressure and other~ise similar conditions, is the eli-mination of alkyl acetates with the formation of mono-alkyl vinylphosphonates and other compounds as residue products. A further advantage of the invention is that it is no~ possible to dispense with the use of the ex-pensive ortho-esters of carboxylic acids for the prepa-ration of pure dialkyl vinylphosphona~es.
The dialkyl vinylphosphonates prepared in accordance ~ith the invention can, if desired, also be purified ?5 further by distiLLation and, instead o~, or after, ~his can also be hydroly ed to vinylphosphonic acid or poly-merizQd ~ithout further treatment.
The invention is illustrated by means of the following examples.
Examples 1) 50 9 of crude vinylphosphonic acid were initialLy placed in a 1 litre stirred flask equipped ~ith an off-take device for the sump and a distillation column moun-ted on the flask ~internal diameter 25 mm, length 0.7 m~
packed ~ith 6 mm R~srhig rings) having ~n automatic re-flux divid~r~ a dis~illation receiver, a cold trap placed ~LZ~7~914 downstream ~low-temperature cooling by means of solid carbon dioxide) and an attached vacuum pump. The flask ~as heated to 210C and 200 9 per hour of dimethyl acetoxyethanepho~phonate ~ere then in~roduced dropwise at Z1n~C and under a pressure of 10 mbaru The reflux ratio in th~ column was set to 0.5.
The distiiiate obtained in the course of 5 hours was 650 9 of a mixture containing 6.0% by ~eight of unreac-ted dimethyl acetoxyethanephosphonate, 30% by ~eight ofdimethyl vinylphosphonate, 1.2X by ~eight of methyl ace-tate and 10~ by weight of acetic acid. 226 9 of a mix-ture containing 78X by weight of methyl acetate, 4% by ~eight of acetic acid and 7% by weight of dimethyl vinyl-phosphonate were obtained in the cold trap. The residue~as 145 9 of a mixture of various vinylphosphonic acid der;vatives which, after heat treatment ~ith water, are once more suitable as a catalyst for the present reac-tion.
The yield of dimethyl vinylphosphonate, relative to di-methyl acetoxyethanephosphonate reacted, ~as 80%.
2) The experimental set-UP ~as as in Example 1. After 50 g of vinylphosphonic acid had been put in and heated up to 210C, a mixture of 95X by ~eight of dimethyl acetoxyethanephosphonate and 5X by ~eight of vinylphos-phonic acid ~as metered in at a rate of approx. 140 g/h under a pressur~ of 10 ~bar~ ~hen constant condit;ons have been set up, the level of the botto~ product in the reaction fLask ~as kept constant at a voLu0e level of approx. 200 ml by continuously discharging sump material into a similarly evacuated vessel. The reflux ra~io in the column ~as set to 1.
5,500 9 ~ere introduced in the course of 40 hours. This gave 30200 9 of distillate, 1~020 9 o~ product from the cold trap and 1,225 9 of material discharged from the sump.
~2~749~
The process according to the invention can be carried 5 out discontinuously, but also, with particular advantage, cont;nuously5 the cleavage produc~s formed, especially the dialkyl vinylphosphonate, being removed cont;nuously from the reaction mixture by distillation~
It ~as surprising that, under the cond;~ions used in accordance w;th the ;nvention, the dialkyl vinyLPhos-phonates are obtained in a single process sta~e and in a high yield, al~hough in the processes of the state of the art the only reaction to take place, under a higher pressure and other~ise similar conditions, is the eli-mination of alkyl acetates with the formation of mono-alkyl vinylphosphonates and other compounds as residue products. A further advantage of the invention is that it is no~ possible to dispense with the use of the ex-pensive ortho-esters of carboxylic acids for the prepa-ration of pure dialkyl vinylphosphona~es.
The dialkyl vinylphosphonates prepared in accordance ~ith the invention can, if desired, also be purified ?5 further by distiLLation and, instead o~, or after, ~his can also be hydroly ed to vinylphosphonic acid or poly-merizQd ~ithout further treatment.
The invention is illustrated by means of the following examples.
Examples 1) 50 9 of crude vinylphosphonic acid were initialLy placed in a 1 litre stirred flask equipped ~ith an off-take device for the sump and a distillation column moun-ted on the flask ~internal diameter 25 mm, length 0.7 m~
packed ~ith 6 mm R~srhig rings) having ~n automatic re-flux divid~r~ a dis~illation receiver, a cold trap placed ~LZ~7~914 downstream ~low-temperature cooling by means of solid carbon dioxide) and an attached vacuum pump. The flask ~as heated to 210C and 200 9 per hour of dimethyl acetoxyethanepho~phonate ~ere then in~roduced dropwise at Z1n~C and under a pressure of 10 mbaru The reflux ratio in th~ column was set to 0.5.
The distiiiate obtained in the course of 5 hours was 650 9 of a mixture containing 6.0% by ~eight of unreac-ted dimethyl acetoxyethanephosphonate, 30% by ~eight ofdimethyl vinylphosphonate, 1.2X by ~eight of methyl ace-tate and 10~ by weight of acetic acid. 226 9 of a mix-ture containing 78X by weight of methyl acetate, 4% by ~eight of acetic acid and 7% by weight of dimethyl vinyl-phosphonate were obtained in the cold trap. The residue~as 145 9 of a mixture of various vinylphosphonic acid der;vatives which, after heat treatment ~ith water, are once more suitable as a catalyst for the present reac-tion.
The yield of dimethyl vinylphosphonate, relative to di-methyl acetoxyethanephosphonate reacted, ~as 80%.
2) The experimental set-UP ~as as in Example 1. After 50 g of vinylphosphonic acid had been put in and heated up to 210C, a mixture of 95X by ~eight of dimethyl acetoxyethanephosphonate and 5X by ~eight of vinylphos-phonic acid ~as metered in at a rate of approx. 140 g/h under a pressur~ of 10 ~bar~ ~hen constant condit;ons have been set up, the level of the botto~ product in the reaction fLask ~as kept constant at a voLu0e level of approx. 200 ml by continuously discharging sump material into a similarly evacuated vessel. The reflux ra~io in the column ~as set to 1.
5,500 9 ~ere introduced in the course of 40 hours. This gave 30200 9 of distillate, 1~020 9 o~ product from the cold trap and 1,225 9 of material discharged from the sump.
~2~749~
After the sump materiaL hac been boiled up ~ith water and the water removed by distillation, the material can be re-employed as a catalyst for cleaving the feed mix-ture. The distillate contained 89g by weight of dimethyl vinylphos~honate and 1O1% by weight of methyl acetate.
The remainder ~as essentially acetic acid.
The product present in ths cold trap con~ained 6Z by weight of di~ethyl vinylphosphonate, approx. 4X by weight of methanol and 3% by weight of acetic acid; the remainder was essentially methyl acetate.
The yield of dimethyl vinylphosphonate, relative to d;-methyl acetoxyethanephosphonate employed, was 80% by weight.
3) The experimental set-up was as in Example 1. After 50 g of crude vinylphosphonic acid had been put in and heated up to 210C, 224 9 per hour of diethyl 2-acetoxy-ethanephosphonate uere added drop~;se under a pressureof 5 mbar. The reflux ratio ~as set to 0.5. 825 9 of distillate containing 74% by ~eight of diethyl vinyl-phosphonate, 21% by ~eight of acetic acid, 2X by ~eighe of diethyl acetoxyethanephosphonate and 1.7X by weight of triethylphosphate ~ere obtained ;n the course of 5 hours.
The product ~180 g) obtained in the cold trap contained 7%
by weight of di~hyl viny~phosphonate, 28% by weight of acetic acid, 55% by ~eight of ethyl acetate and 8% by weight of ethanol. During this time the contents o~ the sump had increased by 115 9.
The remainder ~as essentially acetic acid.
The product present in ths cold trap con~ained 6Z by weight of di~ethyl vinylphosphonate, approx. 4X by weight of methanol and 3% by weight of acetic acid; the remainder was essentially methyl acetate.
The yield of dimethyl vinylphosphonate, relative to d;-methyl acetoxyethanephosphonate employed, was 80% by weight.
3) The experimental set-up was as in Example 1. After 50 g of crude vinylphosphonic acid had been put in and heated up to 210C, 224 9 per hour of diethyl 2-acetoxy-ethanephosphonate uere added drop~;se under a pressureof 5 mbar. The reflux ratio ~as set to 0.5. 825 9 of distillate containing 74% by ~eight of diethyl vinyl-phosphonate, 21% by ~eight of acetic acid, 2X by ~eighe of diethyl acetoxyethanephosphonate and 1.7X by weight of triethylphosphate ~ere obtained ;n the course of 5 hours.
The product ~180 g) obtained in the cold trap contained 7%
by weight of di~hyl viny~phosphonate, 28% by weight of acetic acid, 55% by ~eight of ethyl acetate and 8% by weight of ethanol. During this time the contents o~ the sump had increased by 115 9.
Claims (20)
1. A process for the production of dialkyl esters of vinyl phosphonic acid which comprises subjecting dialkyl esters of
2-acetoxyethane phosphonic acid to cleavage by contacting with a liquid catalytically acting medium at a temperature in the range from 150 to 270°C and under a pressure such that the partial pressures of the total of the components of the reac-tion system is in the range from 1 to 500 mbar, and drawing off the resulting dialkyl esters of vinyl phosphonic acid and other volatile reaction products.
2. A process as claimed in claim 1, wherein the cleavage is carried out at a total pressure above 500 mbar with the provi-so that the differential pressure between the total pressure and the partial pressure of the total of the components of the reaction system results from a gas inert towards the compo-nents of the reaction system under the reaction conditions.
2. A process as claimed in claim 1, wherein the cleavage is carried out at a total pressure above 500 mbar with the provi-so that the differential pressure between the total pressure and the partial pressure of the total of the components of the reaction system results from a gas inert towards the compo-nents of the reaction system under the reaction conditions.
3. A process as claimed in claim 1, wherein the total pres-sure is adjusted in the reaction system to a range of from 1 to 500 mbar.
4. A process as claimed in claim 1 or 2 or 3, wherein the partial pressure of the total of the components of the reac-tion system is in the range of from 5 to 100 mbar.
5. A process as claimed in claim 2, wherein the inert gas is nitrogen, methane or ethane.
6. A process as claimed in claim 1 or 2 or 3, wherein the temperature is in the range of from 180 to 250°C.
7. A process as claimed in claim 1 or 2 or 3, wherein the alkyl groups of the ester each have from 1 to 8 carbon atoms.
8. A process as claimed in claim 1 or 2 or 3, wherein the alkyl groups of the ester each have from 1 to 4 carbon atoms and the partial pressure of the total of the components of the reaction system is in the range of from 5 to 100 mbar.
9. A process as claimed in claim 1 or 2 or 3, wherein the alkyl groups of the ester each have 1 or 2 carbon atoms.
10. A process as claimed in claim 1, wherein an acidic cata-lytically acting medium is used.
11. A process as claimed in clalm 1 or 2 or 10, wherein the catalytically acting medium is applied in an amount of at least 0.1 and at most 20 %, referred to the weight of the dialkyl ester of the acetoxyethane phosphonic acid introduced in the reaction.
12. A process as claimed in claim 1 or 2 or 10, wherein the catalytically acting medium is applied in an amount of at least 1 % and at most 20 %, referred to the weight of the dialkyl ester of the acetoxyethane phosphonic acid introduced in the reaction.
13. A process as clalmed in claim 1 or 2 or 10, wherein the catalytically acting medium is applied in an amount in the range of from 1 to 5 %, referred to the weight of the dialkyl ester of the acetoxyethane phosphonic acid introduced in the reaction.
14. A process as claimed in claim 1 or 2 or 3, wherein an acidic catalytically acting medium is used which has been formed in the reaction as a higher boiling by-product and subsequently been treated with hot water.
15. A process as claimed in claim 1 or 2 or 3, wherein an acidic catalytically acting medium is used which has been formed in the reaction as a higher boiling by-product and subsequently been treated with boiling water for 5 minutes to 2 hours.
16. A process as claimed in claim 1 or 2 or 3, wherein the cleavage products formed are continuously removed from the reaction zone.
17. A process for the production of di-C1-C4-alkyl esters of vinyl phosphonic acid which comprises subjecting di-C1-C4-alkyl esters of 2-acetoxyethane phosphonic acid to cleavage by contacting with a liquid acidic catalytically acting medi-um at a temperature in the range from 180 to 250°C and under a pressure such that the partial pressures of the total of the components of the reaction system is in the range from 5 to 100 mbar, and drawing off the resulting dialkyl esters of vinyl phosphonic acid and other volatile reaction products.
18. A process as claimed in claim 17, wherein the cleavage products formed are continuously removed from the reaction zone.
19. A process as claimed in claim 17, wherein an acidic ca-talytically acting medium is used which has been formed in the reaction as a higher boiling by-product and subsequently been treated with hot water.
20. A process as claimed in claim 17, 18 or 19, wherein the alkyl groups of the ester each have 1 or 2 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3707149.1 | 1987-03-06 | ||
| DE19873707149 DE3707149A1 (en) | 1987-03-06 | 1987-03-06 | METHOD FOR THE PRODUCTION OF VINYLPHOSPHONESEUREDIALKYLESTER |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1297494C true CA1297494C (en) | 1992-03-17 |
Family
ID=6322378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000560543A Expired - Fee Related CA1297494C (en) | 1987-03-06 | 1988-03-04 | Process for the preparation of dialkyl vinylphosphonates |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4894470A (en) |
| EP (1) | EP0281122B1 (en) |
| JP (1) | JP2650947B2 (en) |
| KR (1) | KR950004961B1 (en) |
| CA (1) | CA1297494C (en) |
| DE (2) | DE3707149A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0329595B1 (en) * | 1988-02-19 | 1996-05-08 | Hoechst Aktiengesellschaft | Process for preparing alkyl esters of alkenylphosphinic acid |
| DE4014483A1 (en) * | 1990-05-07 | 1991-11-14 | Basf Ag | METHOD FOR PRODUCING VINYLPHOSPHONIC ACID DERIVATIVES |
| US5281631A (en) * | 1991-12-20 | 1994-01-25 | Arch Development Corp. | Phosphonic acid based ion exchange resins |
| US5576362A (en) * | 1992-04-20 | 1996-11-19 | Denki Kagaku Kogyo Kabushiki Kaisha | Insulating material and a circuit substrate in use thereof |
| DE4342570C1 (en) * | 1993-12-14 | 1995-09-21 | Hoechst Ag | Process for the continuous preparation of vinylphosphonic acid dialkyl esters |
| DE19501336A1 (en) * | 1995-01-18 | 1996-07-25 | Hoechst Ag | Process for the preparation of vinylphosphonic acid dimethyl ester from 2-acetoxyethanephosphonic acid dimethyl ester |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3110975A1 (en) * | 1981-03-20 | 1982-09-30 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING VINYLPHOSPHONIC ACID |
| DE3120437A1 (en) * | 1981-05-22 | 1982-12-09 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING VINYLPHOSPHONIC ACID |
-
1987
- 1987-03-06 DE DE19873707149 patent/DE3707149A1/en not_active Withdrawn
-
1988
- 1988-03-03 US US07/163,797 patent/US4894470A/en not_active Expired - Lifetime
- 1988-03-03 DE DE8888103226T patent/DE3862774D1/en not_active Expired - Lifetime
- 1988-03-03 EP EP88103226A patent/EP0281122B1/en not_active Expired - Lifetime
- 1988-03-04 CA CA000560543A patent/CA1297494C/en not_active Expired - Fee Related
- 1988-03-04 JP JP63049920A patent/JP2650947B2/en not_active Expired - Lifetime
- 1988-03-04 KR KR1019880002246A patent/KR950004961B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE3862774D1 (en) | 1991-06-20 |
| EP0281122A3 (en) | 1990-01-17 |
| KR880011180A (en) | 1988-10-27 |
| US4894470A (en) | 1990-01-16 |
| EP0281122A2 (en) | 1988-09-07 |
| DE3707149A1 (en) | 1988-09-15 |
| KR950004961B1 (en) | 1995-05-16 |
| EP0281122B1 (en) | 1991-05-15 |
| JP2650947B2 (en) | 1997-09-10 |
| JPS63230698A (en) | 1988-09-27 |
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